KR20240005910A - Methods of manufacturing electronic devices - Google Patents

Abstract

A process (A) of preparing a structure including a wafer having a circuit formation surface and an adhesive film bonded to the circuit formation surface side of the wafer, and a process (B) of backgrinding the surface of the wafer opposite to the circuit formation surface side of the wafer. A method for manufacturing an electronic device, comprising at least a step (C) of irradiating the adhesive film with ultraviolet rays and then removing the adhesive film from the wafer, wherein the adhesive film is provided on a base layer and one side of the base layer, Storage modulus E at 100°C when the UV-curable adhesive resin material is provided with an adhesive resin layer composed of an ultraviolet-curable adhesive resin material and the viscoelastic properties are measured using the following procedures (i) and (ii). '(100℃) is 1.0×10 ⁶ to 3.5×10 ⁷ Pa, and E'(100℃)/E'(-15℃) is 2.0×10 ^-3 to 1.5×10 ^-2 , manufacturing of electronic device method.
[Sequence]
(i) A film with a film thickness of 0.2 mm is formed using an ultraviolet curable adhesive resin material, and the film is irradiated with ultraviolet rays with a main wavelength of 365 nm at an irradiation intensity of 100 W/cm ² using a high-pressure mercury lamp in an environment of 25°C. , irradiated with an ultraviolet dose of 1080 mJ/cm ² and cured with ultraviolet rays to obtain a cured film. (ii) For the cured film, the dynamic viscoelasticity is measured at a frequency of 1 Hz, in tensile mode, and at a temperature in the range of -50 to 200°C.

Description

Methods of manufacturing electronic devices

The present invention relates to a manufacturing method of an electronic device.

Among the manufacturing processes of electronic devices, in the process of grinding a wafer, an adhesive film may be attached to the circuit formation surface of the wafer in order to fix the wafer or prevent damage to the wafer.

As such an adhesive film, a film obtained by laminating an adhesive resin layer on a base film is generally used.

With the advancement of high-density packaging technology, there is a demand for thinner semiconductor wafers, and it is required to thinly grind wafers to a thickness of, for example, 50 μm or less.

As one of these thin grinding processes, there is a free dicing method in which a groove of a predetermined depth is formed on one side of the wafer before the wafer grinding process, and then grinding is performed to separate the wafer into pieces. Additionally, there is a pre-stealth method in which a modified area is formed by irradiating a laser inside the wafer before grinding processing, and then grinding is performed to separate the wafer into pieces.

As a technology related to an adhesive film suitable for application to such a free dicing method or a free stealth method, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2014-75560) and Patent Document 2 (Japanese Patent Laid-Open No. 2016-72546) The technology described in (Public Gazette) can be mentioned.

Patent Document 1 describes a surface protection sheet that has an adhesive layer on a base material and satisfies the following requirements (a) to (d).

(a) The Young's modulus of the substrate is 450 MPa or more.

(b) The adhesive layer has a storage modulus of 0.10 MPa or more at 25°C.

(c) The adhesive layer has a storage modulus of 0.20 MPa or less at 50°C.

(d) The thickness of the adhesive layer is 30㎛ or more.

Patent Document 1 states that such a surface protection sheet suppresses the intrusion of water (sludge intrusion) into the protected surface of the workpiece from the gap formed when the workpiece is cut during the backside grinding process of the workpiece, and protects the protected surface of the workpiece. It is stated that it can prevent contamination.

Patent Document 2 has a base resin film and a radiation-curable adhesive layer formed on at least one side of the base resin film, the base resin film has at least one rigid layer having a tensile modulus of elasticity of 1 to 10 GPa, and the adhesive layer An adhesive tape for protecting the surface of a semiconductor wafer is described, characterized in that the peeling force at a peeling angle of 30° after radiation curing is 0.1 to 3.0 N/25 mm.

Patent Document 2 states that, according to this adhesive tape for semiconductor wafer surface protection, in the backside grinding process of a semiconductor wafer using the free dicing method or the free stealth method, kerf shift of the individual semiconductor chips is suppressed and the semiconductor wafer is protected. It is stated that it can be processed without damage or contamination.

Japanese Patent Publication No. 2014-75560 Japanese Patent Publication No. 2016-72546

According to studies by the present inventors, for example, in the manufacturing process of electronic devices, when peeling the adhesive film from the wafer after the backgrind process, adhesive residue is generated on the dicing street (scribe line) on the wafer side. It turns out it's easy to do. In particular, in the manufacturing process of electronic devices using the free dicing method or the free stealth method, when peeling the adhesive film from the wafer (pieced chips) after the backgrind process, adhesive residue is likely to be generated on the wafer side. It turns out.

Specifically, in the pre-dicing method, since an adhesive film is attached to one side of a wafer with a groove provided on one side, adhesive residue is likely to be generated in the groove and/or near the groove. In particular, since grooves are typically cut using blades, microscopic defects are likely to occur in the grooves, which is thought to be a factor in the generation of adhesive residue.

Even in the free stealth method, it is thought that adhesive residue is likely to be generated at the edge of the chip when peeling the adhesive film from the individual wafers (chips).

The present invention has been made in consideration of the above circumstances. One object of the present invention is to suppress “adhesive residue” when peeling the adhesive film from the wafer (or individual chip) after the backgrind process in the manufacture of electronic devices.

The present inventors studied improvements from various viewpoints. As a result, the invention provided below was completed and the above problems were solved.

The present invention is as follows.

One.

A step (A) of preparing a structure comprising a wafer having a circuit formation surface and an adhesive film bonded to the circuit formation surface side of the wafer;

A step (B) of backgrinding a surface of the wafer opposite to the circuit formation surface,

Step (C) of irradiating the adhesive film with ultraviolet rays and then removing the adhesive film from the wafer

A method of manufacturing an electronic device comprising at least,

The adhesive film includes a base layer and an adhesive resin layer made of an ultraviolet curable adhesive resin material provided on one side of the base layer,

For the above ultraviolet curable adhesive resin material, the storage elastic modulus at -15°C when measuring the viscoelastic properties using the following procedures (i) and (ii) is E' (-15°C) and storage at 100°C. When the elastic modulus is E' (100℃),

E' (100°C) is 1.0×10 ⁶ to 3.5×10 ⁷ Pa,

E'(100°C)/E'(-15°C) is 2.0×10 ^-3 to 1.5×10 ^-2 .

[Sequence]

(i) Form a film with a film thickness of 0.2 mm using the above ultraviolet curable adhesive resin material, and irradiate the film with ultraviolet rays with a dominant wavelength of 365 nm using a high-pressure mercury lamp in an environment of 25°C with an intensity of 100 W/cm ² By irradiating with an ultraviolet dose of 1080 mJ/cm ² and curing it with ultraviolet rays, a cured film is obtained.

(ii) For the cured film, the dynamic viscoelasticity is measured at a frequency of 1 Hz, in tensile mode, and at a temperature in the range of -50 to 200°C.

2.

A method of manufacturing the electronic device described in 1.,

E' (-15°C) is 6.0×10 ⁸ to 3.0×10 ⁹ Pa. A method of manufacturing an electronic device.

3.

A method of manufacturing an electronic device according to 1. or 2.,

The process (A) is,

At least one process (A1) selected from the process (A1-1) of half-cutting the wafer and the process (A1-2) of irradiating the wafer with a laser and forming a modified layer on the wafer,

After the step (A1), a step (A2) of attaching the adhesive film to the circuit formation side of the wafer.

A method of manufacturing an electronic device comprising:

4.

A method of manufacturing an electronic device according to any one of 1. to 3.,

In the step (C), the adhesive film is irradiated with ultraviolet rays at a dose of 200 mJ/cm ² or more and 2000 mJ/cm ^{2 or} less to photocure the adhesive resin layer to reduce the adhesive strength of the adhesive resin layer, and then removing the adhesive film from the wafer.

5.

A method of manufacturing an electronic device according to any one of 1. to 4.,

A method of manufacturing an electronic device, wherein the adhesive resin layer includes a (meth)acrylic resin having a polymerizable carbon-carbon double bond in the molecule and a photoinitiator.

6.

A method of manufacturing an electronic device according to any one of 1. to 5.,

A method of manufacturing an electronic device wherein the adhesive resin layer has a thickness of 5 ㎛ or more and 300 ㎛ or less.

7.

A method of manufacturing an electronic device according to any one of 1. to 6.,

The resin constituting the base material layer is polyolefin, polyester, polyamide, poly(meth)acrylate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyetherimide, ethylene/vinyl acetate copolymer, and polyacrylate. A method of manufacturing an electronic device comprising one or more types selected from the group consisting of nitrile, polycarbonate, polystyrene, ionomer, polysulfone, polyethersulfone, polyetheretherketone, and polyphenylene ether.

The electronic device manufacturing method of the present invention makes it possible to suppress adhesive residue when peeling the adhesive film from the wafer (or individual chip) after the backgrind process.

1 is a diagram (cross-sectional view) schematically showing an example of the structure of an adhesive film.
FIG. 2 is a diagram (cross-sectional view) schematically showing an example of a method for manufacturing an electronic device.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention will be described in detail with reference to the drawings.

In all drawings, like components are given the same reference numerals, and descriptions thereof are omitted as appropriate.

In order to avoid complexity, (i) when there are multiple identical components in the same drawing, only one of them is labeled and not all of them are labeled, or (ii) especially after Figure 2, Figures 1 and 2 In some cases, the same component is not labeled again.

All drawings are for explanatory purposes only. The shape, size ratio, etc. of each member in the drawings do not necessarily correspond to the actual product.

In the description of the numerical range in this specification, the notation “X to Y” indicates not less than X but not more than Y, unless otherwise specified. For example, “1 to 5% by mass” means “1% by mass or more and 5% by mass or less.”

In the notation of groups (atomic groups) in this specification, notation that does not describe substitution or unsubstitution includes both those without a substituent and those with a substituent. For example, an “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

The term “(meth)acrylic” in this specification represents a concept that includes both acrylic and methacryl. The same applies to similar notations such as “(meth)acrylate”.

In this specification, the word “organic group” means an atomic group excluding one or more hydrogen atoms from an organic compound, unless otherwise specified. For example, “monovalent organic group” refers to an atomic group excluding one hydrogen atom from an arbitrary organic compound.

The word “electronic device” in this specification refers to devices to which electronic engineering technology is applied, such as semiconductor chips, semiconductor devices, printed wiring boards, electric circuit display devices, information and communication terminals, light-emitting diodes, physical cells, and chemical cells. It is used to include devices, final products, etc.

Fig. 1 is a cross-sectional view schematically showing an example of the structure of an adhesive film (adhesive film 50) preferably used in this embodiment.

The adhesive film 50 is used to protect the surface of the wafer.

As shown in FIG. 1, the adhesive film 50 includes a base layer 10 and an ultraviolet curable adhesive resin layer 20 provided on one side of the base layer 10 (adhesive layer made of an ultraviolet curable adhesive resin material). Resin layer) is provided.

For the adhesive resin layer 20 (adhesive resin layer composed of an ultraviolet curable adhesive resin material), the storage elastic modulus at -15°C when the viscoelastic properties were measured using the following procedures (i) and (ii). E'(-15℃), the storage modulus at 100℃ is called E'(100℃). At this time, E'(100℃) and E'(100℃)/E'(-15℃) satisfy the following.

E' (100℃): 1.0×10 ⁶ to 3.5×10 ⁷ Pa

E'(100℃)/E'(-15℃): 2.0×10 ^-3 to 1.5×10 ^-2

[Sequence]

(i) A film with a film thickness of 0.2 mm is formed using an ultraviolet curable adhesive resin material, and the film is irradiated with ultraviolet rays with a main wavelength of 365 nm at an irradiation intensity of 100 W/cm ² using a high-pressure mercury lamp in an environment of 25°C. , irradiated with an ultraviolet dose of 1080 mJ/cm ² and cured with ultraviolet rays to obtain a cured film.

(ii) For the cured film, the dynamic viscoelasticity is measured at a frequency of 1 Hz, in tensile mode, and at a temperature in the range of -50 to 200°C.

Additionally, E' (-15°C) is preferably in the following range.

E'(-15℃): 6.0×10 ⁸ to 3.0×10 ⁹ Pa

Incidentally, in order to suppress polymerization inhibition by oxygen, when irradiated with ultraviolet rays in (i) above, the film formed using the ultraviolet curable adhesive resin material is bonded to, for example, a release film. Specifically, it is as follows.

· Prepare an ultraviolet curable adhesive resin material with a thickness of 0.2 mm and the same composition as the adhesive resin layer 20.

· The UV-curable adhesive resin material is sandwiched between the silicone release-treated surfaces of a colorless and transparent polyethylene terephthalate film (separator) that has been treated with silicone release on both sides. Examples of the colorless and transparent polyethylene terephthalate film (separator) subjected to silicone mold release treatment include SP-PET T15 and T18 manufactured by Mitsui Chemicals Tocello and Purex A31 and A41 manufactured by Toyobo.

- The obtained sample (three-layer structure of separator/adhesive resin layer 20/separator) was irradiated with ultraviolet rays with a main wavelength of 365 nm using a high-pressure mercury lamp in an environment of 25°C at an intensity of 100 W/cm ² and an ultraviolet ray dose of 1080 mJ. Irradiate with /cm ² and cure with ultraviolet rays.

· After UV curing, the separators on both sides are peeled off to use as a sample for measurement. The size of the sample for measurement is 10 mm in width and 50 mm in length.

· Using a solid viscoelasticity measuring device, set the device so that the chuck spacing is 20 mm, and measure the viscoelasticity at a frequency of 1 Hz, in tensile mode, and at a temperature in the range of -50 to 200°C. Examples of solid viscoelasticity measuring devices include RSA3, manufactured by TA Instruments, and the like.

The lower limit of E' (-15°C) is more preferably 7.0 x 10 ⁸ or more, and the upper limit of E' (-15°C) is more preferably 2.0 x 10 ⁹ or less.

The lower limit of E' (100°C) is preferably 5.0 x 10 ⁶ or more, and the upper limit of E' (100°C) is preferably 2.0 x 10 ⁷ or less.

The value of E'(-15°C)/E'(100°C) is preferably in the range of 3.0×10 ^-3 to 1.5×10 ^-2 .

The relationship between the above viscoelastic properties and suppression of adhesive residue can be explained as follows. For the sake of explanation, the present invention is not limited by the following description.

Regarding the dynamic viscoelasticity of polymers, the change in frequency is very similar to the change in temperature, and it is known that increasing the frequency and lowering the temperature have the same effect (time-temperature conversion law).

When peeling the adhesive film, the cured film of the adhesive resin layer is momentarily greatly deformed. Therefore, it is thought that the viscoelastic behavior in the high frequency region (i.e., low temperature region) corresponds well to the actual peeling mode. Furthermore, based on the inventors' past knowledge, etc., it is believed that the viscoelastic behavior in the low frequency region (i.e., high temperature region) reflects the crosslinked state of the cured film of the adhesive resin layer.

Peeling of the adhesive film after curing is usually performed at room temperature, but the storage elastic modulus at a high temperature of about 100°C, and the ratio of (storage elastic modulus at a low temperature of about -15°C) and (storage elastic modulus at a high temperature of about 100°C) It is estimated that E'(100°C)/E'(-15°C) may be closely related to the peeling mode. More specifically, it is as follows.

Regarding elastic modulus at 100°C: The temperature of 100°C is a sufficiently high temperature relative to the glass transition temperature of the adhesive material, and the amorphous adhesive material is considered to be in a completely amorphous state. Therefore, E' (100°C) is thought to represent the crosslinking density of the adhesive material. If E' (100°C) is too high, the crosslinking density of the adhesive material is too high, the toughness is significantly impaired, and the adhesive material becomes embrittled and prone to fracture, so it is presumed that adhesive residue is likely to be generated. In addition, if E' (100°C) is too low, it means that the crosslinking density is too low, and the interaction between the adhesive and the adherend is too large to make peeling difficult, so it is presumed that adhesive residue is likely to be generated.

Regarding the elastic modulus at low temperatures: It is known that the change in frequency is very similar to the change in temperature, and increasing the frequency and lowering the temperature have the same effect (time-temperature conversion law). It is known that the adhesive material is greatly deformed instantaneously when the tape is peeled, and it is thought that the viscoelastic behavior in the region where the frequency is higher (i.e., the lower temperature region) is close to the actual peel mode. Since tape peeling is usually performed at room temperature, the influence of the storage modulus E' at a lower temperature, for example, -15°C, can be considered. And, if the ratio of E' (100°C) and E' (-15°C) described above is within a specific range, it is estimated that peeling proceeds smoothly and adhesive material is unlikely to remain.

In other words, if E'(100℃)/E'(-15℃) is too low, E'(-15℃) is relatively high and the adhesive material is too hard during actual peeling, so it may become embrittled and fracture. It is presumed that it is easy to generate adhesive residue. Additionally, when E'(100℃)/E'(-15℃) is too high, E'(-15℃) is relatively small and the adhesive material is too flexible during actual peeling, so the adhesive material and the adherend adhere to each other. It is presumed that the interaction between the materials is high, making it difficult to peel, and making adhesive residue more likely to occur.

As mentioned above, the fact that E'(100°C) is an appropriate value corresponds to the fact that the adhesive material has an appropriate crosslinking density that makes it difficult for adhesive residue to form, and the fact that E'(100°C)/E'(-15°C) is an appropriate value means that It is assumed that the crosslinking density and toughness of the adhesive are appropriate, contributing to the reduction of adhesive residue.

For reference, the estimate for E' (-15°C) is also listed.

Regarding the elastic modulus at -15°C: It is known that the change in frequency is very similar to the change in temperature, and increasing the frequency and lowering the temperature have the same effect (time-temperature conversion law). It is known that when the tape is peeled, the adhesive material is greatly deformed instantaneously, and the viscoelastic behavior in the region where the frequency is higher (i.e., the lower temperature region) is believed to be close to the actual peel mode. Therefore, although tape peeling is usually performed at room temperature, it is presumed that the storage elastic modulus E' at a lower temperature of -15°C well represents the behavior of the adhesive material when the tape is actually peeled. For this reason, it is estimated that adhesive residue can be further suppressed by designing the adhesive material so that E' (-15°C) is an appropriate value.

The adhesive film 50 that satisfies the above storage modulus requirements can be manufactured by appropriately selecting materials, appropriate mixing of each material, and manufacturing conditions. Details of these will be described below.

Hereinafter “1. In the section “Adhesive Film,” each layer constituting the adhesive film 50 is explained in detail.

1. Adhesive film

(Base layer)

The base material layer 10 is a layer provided for the purpose of improving the properties of the adhesive film 50, such as handling, mechanical properties, and heat resistance.

The base material layer 10 is not particularly limited as long as it has mechanical strength that can withstand the external force applied when processing the wafer, and examples include resin films.

Examples of the resin constituting the base material layer 10 include polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene); Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyamides such as nylon-6, nylon-66, and polymethoxylene adipamide; (meth)acrylic resins such as polyacrylate and polymethacrylate; polyvinyl chloride; polyvinylidene chloride; polyimide; polyetherimide; Ethylene/vinyl acetate copolymer; polyacrylonitrile; polycarbonate; polystyrene; ionomer; polysulfone; polyethersulfone; polyetheretherketone; One or two or more types selected from polyphenylene ether and the like can be mentioned.

Among these, from the viewpoint of improving mechanical properties and transparency, one selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, ethylene-vinyl acetate copolymer, and polybutylene terephthalate. One type or two or more types are preferable, and one type or two or more types selected from polyethylene terephthalate and polyethylene naphthalate are more preferable.

The base material layer 10 may be a single layer or two or more types of layers.

In addition, the form of the resin film used to provide the base material layer 10 may be a stretched film, or may be a film stretched in the uniaxial direction or the biaxial direction. From the viewpoint of improving the mechanical strength of the base layer 10, it is preferable that the film is stretched in uniaxial or biaxial directions.

The base material layer 10 is preferably annealed in advance from the viewpoint of suppressing warpage of the wafer after grinding. The base layer 10 may be surface treated to improve adhesion to other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coat treatment, etc. may be performed.

From the viewpoint of obtaining good film properties, the thickness of the base layer 10 is preferably 20 μm or more and 250 μm or less, more preferably 30 μm or more and 200 μm or less, and even more preferably 50 μm or more and 150 μm or less.

(Adhesive resin layer)

The adhesive film 50 includes an ultraviolet curing adhesive resin layer 20.

The adhesive resin layer 20 is a layer provided on one side of the base layer 10, and is a layer that is in contact with and adheres to the circuit formation surface of the wafer when the adhesive film 50 is attached to the circuit formation surface of the wafer.

The adhesive resin layer 20 is formed using a suitable ultraviolet curable adhesive resin material. Specifically, the adhesive resin layer 20 is formed using an ultraviolet curable adhesive resin material whose adhesive strength is reduced by ultraviolet rays.

When the adhesive resin layer 20 is irradiated with ultraviolet rays, it hardens (crosslinks, etc.) and the adhesive strength decreases, making it easier to peel the wafer (or the chip into which the wafer is divided) from the adhesive film 50.

The ultraviolet curable adhesive resin material preferably contains a (meth)acrylic resin known in the field of adhesives, adhesives, etc.

Examples of the (meth)acrylic resin include a homopolymer of a (meth)acrylic acid ester compound and a copolymer of a (meth)acrylic acid ester compound and a comonomer. Examples of the (meth)acrylic acid ester compound as a raw material monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and hydroxyethyl (meth)acrylate. ) acrylate, hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, etc. These (meth)acrylic acid ester compounds may be used individually or in combination of two or more types.

In addition, examples of comonomers constituting the (meth)acrylic copolymer include vinyl acetate, (meth)acrylnitrile, styrene, (meth)acrylic acid, itaconic acid, (meth)acrylamide, and methylol (meth)acrylamide. , maleic anhydride, etc. When using these comonomers, one type may be used individually, or two or more types may be used in combination.

The ultraviolet curable adhesive resin material preferably contains a (meth)acrylic resin having a polymerizable carbon-carbon double bond at the side chain and/or terminal, a photoinitiator, and, if necessary, a crosslinking agent, etc. The ultraviolet curable adhesive resin material may further contain a low molecular weight compound (such as a polyfunctional (meth)acrylate compound) having two or more polymerizable carbon-carbon double bonds in one molecule.

A (meth)acrylic resin having a polymerizable carbon-carbon double bond at the side chain and/or terminal is specifically obtained as follows. First, a monomer having an ethylenic double bond and a copolymerizable monomer having a functional group (P) are copolymerized. Next, the functional group (P) contained in this copolymer is reacted with a monomer having a functional group (Q) that can cause an addition reaction, condensation reaction, etc. with the functional group (P) while leaving the double bond in the monomer, and the copolymer is formed. Introduces a polymerizable carbon-carbon double bond into the molecule.

Monomers having an ethylenic double bond include, for example, alkyl acrylates and alkyl methacrylates such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, butyl (meth)acrylate, and ethyl (meth)acrylate. One or two or more types are used among monomers, vinyl esters such as vinyl acetate, and monomers having an ethylenic double bond such as (meth)acrylonitrile, (meth)acrylamide, and styrene.

Examples of copolymerizable monomers having a functional group (P) include (meth)acrylic acid, maleic acid, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, N-methylol (meth)acrylamide, and (meth)acrylic acid. Acryloyloxyethyl isocyanate, etc. can be mentioned. These may be one type or may be used in combination of two or more types.

The ratio of the monomer having an ethylenic double bond to the copolymerizable monomer having a functional group (P) is 70 to 99% by mass for the monomer having an ethylenic double bond, and 1 to 30% by mass of the copolymerizable monomer having a functional group (P). % is preferable. More preferably, the monomer having an ethylenic double bond is 80 to 95% by mass, and the copolymerizable monomer having a functional group (P) is 5 to 20% by mass.

Examples of the monomer having a functional group (Q) include the same monomer as the copolymerizable monomer having the functional group (P).

A combination of a functional group (P) and a functional group (Q) reacted when introducing a polymerizable carbon-carbon double bond into a copolymer of a monomer having an ethylenic double bond and a copolymerizable monomer having a functional group (P), comprising a carboxyl group A combination in which an addition reaction occurs easily, such as an epoxy group, a carboxyl group, an aziridinyl group, a hydroxyl group, and an isocyanate group, is preferred. In addition, it is not limited to addition reaction, and any reaction that can easily introduce a polymerizable carbon-carbon double bond, such as a condensation reaction of a carboxylic acid group and a hydroxyl group, can be applied.

When copolymerizing a monomer having an ethylenic double bond and a copolymerizable monomer having a functional group (P), a polymerization initiator can be used. Examples of the polymerization initiator include radical polymerization initiators such as benzoyl peroxide polymerization initiator and t-butylperoxy-2-ethylhexanoate.

Examples of low molecular weight compounds having two or more polymerizable carbon-carbon double bonds in one molecule include tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tetramethylolmethane tetraacrylate. , pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylol and polyfunctional (meth)acrylate compounds such as propane tetraacrylate. When using these, only one type may be used, or two or more types may be used. The amount of the low molecular weight compound having two or more polymerizable carbon-carbon double bonds in the molecule is preferably 0.1 to 20 parts by mass, more preferably 5 to 18 parts by mass, based on 100 parts by mass of the (meth)acrylic resin. It is wealth.

In addition, the amount of the low molecular weight compound having two or more polymerizable carbon-carbon double bonds in the molecule is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the (meth)acrylic resin. , more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 18 parts by mass or less, more preferably 15 parts by mass or less, even more preferably is 13 parts by mass or less.

Photoinitiators are usually irradiated with ultraviolet rays to generate chemical species (radicals, etc.) that polymerize polymerizable carbon-carbon double bonds.

Examples of the photoinitiator include benzoin, isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, Acetophenone diethyl ketal, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-4'-mor Polynobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1 -On, etc. can be mentioned.

Only one type of photoinitiator may be used, or two or more types may be used.

The amount of the photoinitiator added is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 4 to 10 parts by mass, based on 100 parts by mass of the (meth)acrylic resin.

Additionally, the amount of the photoinitiator added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and even more preferably 4 parts by mass, based on 100 parts by mass of the (meth)acrylic resin. parts or more, more preferably 5 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12 parts by mass or less, further preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.

The ultraviolet curable adhesive resin material may contain a crosslinking agent.

Examples of crosslinking agents include epoxy compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and diglycerol polyglycidyl ether, and tetramethylolmethane-tri- β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxylamide), N, Aziridine-based compounds such as N'-hexamethylene-1,6-bis(1-aziridinecarboxyamide), and isocyanate-based compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, and polyisocyanate.

Only one type of crosslinking agent may be used, or two or more types may be used.

When using a crosslinking agent, the amount is usually preferably within a range such that the number of functional groups in the crosslinking agent does not exceed the number of functional groups in the (meth)acrylic resin. However, it may be contained in excess as needed, such as when a new functional group is generated through a crosslinking reaction or when the crosslinking reaction is slow.

When using a crosslinking agent, the content of the crosslinking agent in the ultraviolet curable adhesive resin material is 0.1 part by mass or more per 100 parts by mass of the (meth)acrylic resin from the viewpoint of improving the balance of heat resistance and adhesion of the adhesive resin layer 20. 15 It is preferable that it is 0.5 parts by mass or more and 5 parts by mass or less.

In addition, when using a crosslinking agent, the content of the crosslinking agent in the ultraviolet curable adhesive resin material is preferably set to 100 parts by mass of the (meth)acrylic resin from the viewpoint of improving the balance of heat resistance and adhesion of the adhesive resin layer 20. 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less. , more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less.

The adhesive resin layer 20 can be formed, for example, by applying an ultraviolet curable adhesive resin material on one side of the base layer 10. That is, the adhesive resin layer 20 can be prepared by applying an ultraviolet curable adhesive resin material prepared by dissolving or dispersing each of the above components in an appropriate solvent (typically an organic solvent) onto one side of the base layer 10. You can.

As the application method, for example, conventionally known application methods such as the roll coater method, reverse roll coater method, gravure roll method, bar coat method, comma coater method, and die coater method can be adopted. Drying conditions are not particularly limited, but it is generally preferable to dry for 10 seconds to 10 minutes in a temperature range of 80 to 200°C. More preferably, it is dried at 80 to 170°C for 15 seconds to 5 minutes. In order to sufficiently promote the crosslinking reaction between the crosslinking agent and the (meth)acrylic resin, after drying of the adhesive coating liquid is completed, it may be heated at 40 to 80°C for about 5 to 300 hours.

As a method different from applying an ultraviolet curable adhesive resin material on one side of the base layer 10, as shown in the examples published later, (i) first, the ultraviolet curable adhesive resin material is applied to the easily peelable substrate. A method of applying the adhesive to the surface of the separator to form the adhesive resin layer 20, and (ii) subsequently bonding the formed adhesive resin layer to one side of the base material layer 10, may be used.

The thickness of the adhesive resin layer 20 is preferably 5 μm or more and 300 μm or less, more preferably 10 μm or more and 100 μm or less, and even more preferably 10 μm or more and 50 μm or less.

In addition, the thickness of the adhesive resin layer 20 is preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and preferably 300 μm or less, more preferably 100 μm or less. , more preferably 50㎛ or less.

When the thickness of the adhesive resin layer 20 is appropriately large, sufficient adhesiveness is obtained. Additionally, when the adhesive resin layer 20 is not too thick, the handleability of the adhesive film 50 is improved.

(Other floors)

The adhesive film 50 may include other layers as long as the effect of suppressing adhesive residue is not impaired. For example, there may be other layers such as an uneven water absorbent resin layer, an adhesive layer, or an antistatic layer between each layer. By forming the uneven absorbent resin layer, the uneven absorbent property of the adhesive film 50 can be improved. By forming an adhesive layer, the adhesiveness between each layer can be improved. Additionally, providing an antistatic layer can improve the antistatic properties of the adhesive film 50.

Additionally, from the viewpoint of suppressing deterioration or adhesion of foreign substances before use, the exposed surface of the adhesive resin layer 20 may be protected with a suitable protective film (easily peelable film) such as a release film.

(total thickness)

The overall thickness of the adhesive film 50 is preferably 50 μm or more and 600 μm or less, more preferably 50 μm or more and 400 μm or less, and even more preferably 50 μm or more and 300 μm, from the balance of mechanical properties and handleability. It is as follows.

(Decreased adhesion due to exposure to ultraviolet rays)

As described above, in the adhesive film 50, the adhesive resin layer 20 is formed using an ultraviolet curable adhesive resin material whose adhesive strength is reduced by ultraviolet rays.

The degree to which adhesive strength is reduced by ultraviolet rays is preferably quantified as follows.

· Peeling when the adhesive resin layer 20 of the adhesive film 50 is bonded to a mirror-polished silicon wafer, left for 1 hour, and then subjected to a peeling test under the conditions of a peeling angle of 180° and a peeling speed of 300 mm/min. The intensity is called F0.

The adhesive resin layer 20 of the adhesive film 50 is bonded to a mirror-polished silicon wafer, irradiated with 1080 mJ/cm ² of ultraviolet rays with a wavelength of 365 nm, and then peeled at a peeling angle of 180° and a peeling speed of 300 mm/min. The peeling strength when a peeling test is performed under these conditions is referred to as F1.

·F1/F0 is preferably 0.01 to 0.60, more preferably 0.01 to 0.20, and still more preferably 0.02 to 0.20.

Furthermore, F1/F0 is preferably 0.01 or more, more preferably 0.015 or more, more preferably 0.02 or more, and preferably 0.60 or less, more preferably 0.30 or less, even more preferably 0.20 or less. Preferably it is 0.15 or less, more preferably 0.12 or less.

When F1/F0 is an appropriate value, positional misalignment of the wafer during the backgrind process is suppressed, and peeling of the adhesive film 50 becomes easy after the backgrind process.

Incidentally, the value of F0 itself is, for example, 3 to 20 N/25 mm, specifically 3 to 16 N/25 mm.

Additionally, the value of F1 itself is, for example, 10 N/25 mm or less, specifically 1 N/25 mm or less, and more specifically 0.5 N/25 mm or less. F1 may be zero, but F1 is usually 0.005 N/25 mm or more, specifically 0.01 N/25 mm or more.

2. Method of manufacturing electronic devices

FIG. 2 is a cross-sectional view schematically showing an example of a method of manufacturing an electronic device using the adhesive film 50.

The manufacturing method of an electronic device includes, for example, at least the following three processes.

(A) A process of preparing a structure 100 including a wafer 30 having a circuit formation surface 30A and an adhesive film 50 bonded to the circuit formation surface 30A side of the wafer 30.

(B) backgrinding the surface of the wafer 30 opposite to the circuit formation surface 30A;

(C) A process of removing the adhesive film 50 from the wafer 30 after irradiating the adhesive film 50 with ultraviolet rays.

In this series of processes, as the adhesive film 50, the above “1. Use the adhesive film described in the section “Adhesive film.” The electronic device manufacturing method of this embodiment is characterized in that the adhesive film 50 is used as a so-called backgrind tape when grinding the back surface of the wafer 30.

Hereinafter, each process of the electronic device manufacturing method will be described.

(Process (A))

First, a structure 100 including a wafer 30 having a circuit formation surface 30A and an adhesive film 50 bonded to the circuit formation surface 30A side of the wafer 30 is prepared.

This structure 100 is formed, for example, by peeling the release film from the adhesive resin layer 20 of the adhesive film 50, exposing the surface of the adhesive resin layer 20, and placing it on the adhesive resin layer 20. , can be manufactured by attaching the circuit formation surface 30A of the wafer 30.

Here, the conditions for attaching the circuit formation surface 30A of the wafer 30 to the adhesive film 50 are not particularly limited, but for example, the temperature is 20 to 80 ° C., the pressure is 0.05 to 0.5 MPa, and the attachment speed is can be 0.5 to 20 mm/sec.

Process (A) is selected from the process (A1-1) of half-cutting the wafer 30 and the process (A1-2) of irradiating the wafer 30 with a laser and forming a modified layer on the wafer 30. It further includes at least one process (A1) and a process (A2) of attaching the adhesive film 50 for backgrinding to the circuit formation surface 30A side of the wafer 30 after the process (A1). desirable.

As described above, the adhesive film 50 according to the present embodiment can be suitably used in an electronic device manufacturing process using a free dicing method, a free stealth method, or the like. Therefore, a manufacturing method that performs the above step (A1-1), which is a free dicing method, or the above step (A1-2), which is a free stealth method, is preferable.

In step (A2), the adhesive film 50 can be heated and attached to the circuit formation surface 30A of the wafer 30. As a result, the adhesive state of the adhesive resin layer 20 and the wafer 30 can be maintained well over a long period of time. The heating temperature is not particularly limited, but is, for example, 60 to 80°C.

The operation of sticking the adhesive film 50 to the wafer 30 may be performed by human hands, but can generally be performed using a device called an automatic sticking machine equipped with a roll-shaped adhesive film.

The wafer 30 attached to the adhesive film 50 is not particularly limited, but is preferably a wafer 30 having a circuit formation surface 30A. For example, semiconductor wafers, epoxy mold wafers, epoxy mold panels, etc. are included, and semiconductor wafers and epoxy mold wafers are preferred.

Additionally, semiconductor wafers include, for example, silicon wafers, sapphire wafers, germanium wafers, germanium-arsenic wafers, gallium-phosphorus wafers, gallium-arsenic-aluminum wafers, gallium-arsenic wafers, lithium tantalate wafers, etc. Suitable for use on silicon wafers. Examples of the epoxy mold wafer include wafers manufactured by the eWLB (Embedded Wafer Level Ball Grid Array) process, which is one of the fan-out type WLP manufacturing methods.

Semiconductor wafers and epoxy mold wafers having a circuit formation surface are not particularly limited, and examples include those with circuits such as wiring, capacitors, diodes, or transistors formed on the surface. Additionally, the circuit formation surface may be subjected to plasma treatment.

The circuit formation surface 30A of the wafer 30 may be an uneven surface by, for example, having bump electrodes or the like.

For example, when mounting an electronic device on a mounting surface, the bump electrode is bonded to an electrode formed on the mounting surface to form an electrical connection between the electronic device and the mounting surface (a mounting surface such as a printed board).

Examples of bump electrodes include ball bumps, printing bumps, stud bumps, plating bumps, and filler bumps. That is, the bump electrode is typically a convex electrode. These bump electrodes may be used individually or in combination of two or more types.

The height and diameter of the bump electrode are not particularly limited, but are each preferably 10 to 400 μm, more preferably 50 to 300 μm. The bump pitch at that time is not particularly limited, but is preferably 20 to 600 μm, more preferably 100 to 500 μm.

The metal species constituting the bump electrode is not particularly limited, and examples include solder, silver, gold, copper, tin, lead, bismuth, and alloys thereof. However, in the adhesive film 50, the bump electrode is a solder bump. It is suitably used in this case. These metal species may be used individually or in combination of two or more types.

(Process (B))

Next, the surface (also referred to as the back surface) of the wafer 30 opposite to the circuit formation surface 30A is backgrinded.

“Back grinding” means thinning the wafer 30 to a predetermined thickness without damaging it.

For example, the structure 100 is fixed to a chuck table of a grinding machine, etc., and the back side (non-circuit forming surface) of the wafer 30 is ground.

In this back grinding operation, the wafer 30 is ground until its thickness is below the desired thickness. The thickness of the wafer 30 before grinding is appropriately determined by the diameter and type of the wafer 30, and the thickness of the wafer 30 after grinding is appropriately determined by the size of the chip obtained, the type of circuit, etc.

In addition, when the wafer 30 is half-cut or a modified layer is formed by laser irradiation, the wafer 30 is divided into pieces by process (B) as shown in FIG. 2, and the chips 31 ) becomes.

The back grinding method is not particularly limited, and a known grinding method can be adopted. Grinding can be performed by spraying water on the wafer 30 and the grindstone to cool them. If necessary, a dry polish process, which is a grinding method that does not use grinding water, can be performed at the end of the grinding process.

After the back side grinding is completed, chemical etching is performed as necessary. Chemical etching involves attaching the adhesive film 50 to an etching solution selected from the group consisting of an acidic aqueous solution consisting of hydrofluoric acid, nitric acid, sulfuric acid, acetic acid, etc. alone or in a mixture, and an alkaline aqueous solution such as an aqueous potassium hydroxide solution and an aqueous sodium hydroxide solution. This is done by a method such as immersing the wafer 30 in a wet state. Etching is performed for the purposes of removing strain generated on the back surface of the wafer 30, further thinning the wafer 30, removing oxide films, etc., and preprocessing when forming electrodes on the back surface. The etching solution is appropriately selected depending on the above purpose.

(Process (C))

Next, after irradiating ultraviolet rays to the adhesive film 50, the adhesive film 50 is removed from the wafer 30. In step (C), the adhesive film 50 is irradiated with ultraviolet rays at a dose of, for example, 200 mJ/cm ² or more and 2000 mJ/cm ² or less, thereby curing the adhesive resin layer 20 with ultraviolet rays to form the adhesive resin layer 20. ) to reduce the adhesive force, and then the adhesive film 50 is removed from the wafer 30.

Ultraviolet irradiation can be performed using, for example, ultraviolet rays with a dominant wavelength of 365 nm using a high-pressure mercury lamp.

The irradiation intensity of ultraviolet rays is, for example, 50 mW/cm ² or more and 500 mW/cm ² or less.

Before removing the adhesive film from the wafer 30, the wafer 30 may be mounted together with the ring frame on a dicing tape or a dicing tape with a die attach film. The operation of removing the adhesive film 50 from the wafer 30 may be performed manually, but can generally be performed using a device called an automatic peeler.

The surface of the wafer 30 after peeling off the adhesive film 50 may be cleaned as needed. Examples of cleaning methods include wet cleaning such as water cleaning and solvent cleaning, and dry cleaning such as plasma cleaning. In the case of wet cleaning, ultrasonic cleaning may be used together. The cleaning method can be appropriately selected depending on the contamination condition of the surface of the wafer 30.

(Other processes)

After performing steps (A) to (C), a step of mounting the obtained chip 31 on a circuit board may be further performed. These processes can be performed based on known information.

Although embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope of achieving the purpose of the present invention are included in the present invention.

Example

Embodiments of the present invention will be described in detail based on examples and comparative examples. For the sake of explanation, the present invention is not limited to the examples.

In examples, the exponent notation may be indicated by the symbol “E”. For example, the notation 1.3E+06 means 1.3×10 ⁶ .

<Preparation of raw materials>

The following raw materials were prepared.

(Base layer)

Base layer 1: Polyethylene terephthalate film (manufactured by Toyobo, product name: E7180, thickness: 50㎛, single-sided corona treated product)

Base layer 2: A laminated film made of low-density polyethylene film/polyethylene terephthalate film/low-density polyethylene film (total thickness: 110 μm) prepared as follows.

It was obtained by laminating a low-density polyethylene film (density: 0.925 kg/m ³ , thickness: 30 μm) on both sides of a polyethylene terephthalate film (manufactured by Toray, product name: Lumiror S10, thickness: 50 μm). Corona treatment was performed on one side of the obtained laminated film.

Base layer 3: Laminated film consisting of polyethylene terephthalate film/ethylene/vinyl acetate copolymer film/acrylic film (total thickness: 145 μm) prepared as follows.

Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: E7180, thickness: 50 ㎛) and ethylene/vinyl acetate copolymer (manufactured by Mitsui Dow Polychemical Co., Ltd., MFR: 2.5 g/10 min.) film (thickness: 70 ㎛), The ethylene/vinyl acetate copolymer film was laminated by corona treatment on the bonding surface side with the polyethylene terephthalate film. In addition, corona discharge treatment was also performed on the opposite side of the polyethylene terephthalate film of the ethylene-vinyl acetate copolymer film.

Next, the acrylic resin coating liquid for the base material layer shown below is coated and dried on the release surface of the polyethylene terephthalate film (separator) that has been subjected to the mold release treatment to a dry thickness of 20 μm, and the polyethylene terephthalate film/ethylene/vinyl acetate copolymer is coated and dried. A laminated film made of a polymer film was bonded through an ethylene/vinyl acetate copolymer film and aged (40°C, 3 days). After that, the separator was peeled off.

As described above, base material layer 3 was obtained.

(Acrylic resin coating liquid for base layer)

As a polymerization initiator, 0.5 parts by mass of 4,4'-azobis-4-cyanovaleric acid (manufactured by Otsuka Chemical Co., Ltd., product name: ACVA) was used, 74 parts by mass of butyl acrylate, 14 parts by mass of methyl methacrylate, and meta An aqueous solution of 9 parts by mass of 2-hydroxyethyl acrylate, 2 parts by mass of methacrylic acid, 1 part by mass of acrylamide, and polyoxyethylenenonylpropenylphenyl ether ammonium sulfate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Aqualon HS) -1025) 3 parts by mass were emulsion polymerized in deionized water at 70°C for 9 hours. After completion of polymerization, pH was adjusted to 7 with ammonia water to obtain an acrylic polymer aqueous emulsion with a solid content concentration of 42.5% by mass. Next, with respect to 100 parts by mass of this acrylic polymer water-based emulsion, pH was adjusted to 9 or more using aqueous ammonia, and 0.75 parts by mass of an aziridine-based crosslinking agent [Chemitite PZ-33, manufactured by Nippon Shokubai Chemicals Co., Ltd.] and 5 parts by mass of diethylene glycol monobutyl ether were blended.

As described above, an acrylic resin coating liquid for the base material layer was obtained.

((meth)acrylic resin solution)

(meth)acrylic resin solution 1:

49 parts by mass of ethyl acrylate, 20 parts by mass of 2-ethylhexyl acrylate, 21 parts by mass of methyl acrylate, 10 parts by mass of glycidyl methacrylate, and 0.5 parts by mass of a benzoyl peroxide-based polymerization initiator (in terms of solid content) as a polymerization initiator. , was reacted at 80°C for 10 hours in a mixed solvent of 65 parts by mass of toluene and 50 parts by mass of ethyl acetate. After completion of the reaction, the obtained solution was cooled, 25 parts by mass of xylene, 5 parts by mass of acrylic acid, and 0.5 parts by mass of tetradecyldimethylbenzylammonium chloride were added to the cooled solution, and the reaction was performed at 85°C for 32 hours while blowing air.

As described above, (meth)acrylic resin solution 1 was obtained.

(meth)acrylic resin solution 2:

77 parts by mass of n-butyl acrylate, 16 parts by mass of methyl methacrylate, 16 parts by mass of 2-hydroxyethyl acrylate, 0.3 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and 20 parts by mass of toluene. and 80 parts by mass of ethyl acetate in a mixed solvent at 85°C for 10 hours. After completion of the reaction, the obtained solution was cooled, and 30 parts by mass of toluene, 7 parts by mass of methacryloyloxyethyl isocyanate (manufactured by Showa Denko, product name: Karenz MOI), and 0.05 parts by mass of dibutyltin dilaurate were added thereto. , reaction was performed at 85°C for 12 hours while blowing air.

As described above, (meth)acrylic resin solution 2 was obtained.

(meth)acrylic resin solution 3:

30 parts by mass of ethyl acrylate, 11 parts by mass of methyl acrylate, 26 parts by mass of 2-ethylhexyl acrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, and 0.8 parts by mass of benzoyl peroxide-based polymerization initiator as a polymerization initiator (in terms of solid content) ) was reacted at 80°C for 9 hours in a mixed solvent of 7 parts by mass of toluene and 50 parts by mass of ethyl acetate. After completion of the reaction, the obtained solution was cooled, and 25 parts by mass of toluene was added to the cooled solution.

As described above, (meth)acrylic resin solution 3 was obtained.

(Photoinitiator)

Omnirad 651 (manufactured by IGM): 2,2-dimethoxy-2-phenylacetophenone

Omnirad 369 (manufactured by IGM): 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone

(Multifunctional (meth)acrylate)

Aronix M400 (manufactured by Doua Kousei): mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

(Cross-linking agent)

Isocyanate-based crosslinking agent (manufactured by Mitsui Chemicals, brand name: Oresta P49-75S)

<Preparation of ultraviolet curable adhesive resin material (coating liquid for forming adhesive resin layer)>

Each material described in the column of “UV-curable adhesive resin material (coating liquid for forming an adhesive resin layer)” in Table 1 was mixed uniformly to obtain an ultraviolet-curable adhesive resin material (coating liquid for forming an adhesive resin layer).

<Measurement of cured film viscoelasticity of ultraviolet curable adhesive resin material>

First, the ultraviolet curable adhesive resin material (coating liquid for forming the adhesive resin layer) shown in Table 1 was replaced with a silicone mold release-treated polyethylene terephthalate film (separator) (SP-PET T18 (thickness 31 μm) manufactured by Mitsui Chemical Tocello Co., Ltd.) applied to. Next, it was dried at 120°C for 3 minutes to form an adhesive resin layer with a thickness of 30 to 40 μm. By overlapping several layers of the obtained adhesive resin layers, a laminate sample having a separator/0.2 mm thick adhesive resin layer/separator configuration was obtained. The obtained laminate sample was aged by heating in an oven at 40°C for 3 days.

The obtained laminate sample (separator/adhesive resin layer/separator configuration) was irradiated with ultraviolet rays with a dominant wavelength of 365 nm at an irradiation intensity of 100 W/cm ² and an ultraviolet ray dose of 1080 mJ/cm ² using a high-pressure mercury lamp in an environment of 25°C. and cured with ultraviolet rays.

Next, the viscoelasticity was measured using a solid viscoelasticity measuring device (RSA3, manufactured by TA Instruments). Specifically, the cured laminate sample was cut to a width of 10 mm and a length of 50 mm, and the separators on both sides of the cured laminate sample were removed to obtain a measurement sample. After that, the measurement sample was set in the device so that the spacing between the chucks was 20 mm. Then, dynamic viscoelasticity was measured at a frequency of 1 Hz, in tensile mode, and at a temperature range of -50 to 200°C.

<Production of adhesive film>

First, the ultraviolet curable adhesive resin material (coating liquid for forming adhesive resin layer) shown in Table 1 was applied to a polyethylene terephthalate film (separator) that had been treated with silicone mold release. Then, it was dried at 120°C for 3 minutes to form an adhesive resin layer with a thickness of 20 μm.

The formed adhesive resin layer was bonded to the base layer to form a laminate. Specifically, when base layer 1 or 2 was used as the base layer, it was bonded to the corona-treated surface. When base layer 3 was used as the base layer, the separator was peeled and bonded to the acrylic film layer side.

The obtained laminate was aged by heating in an oven at 40°C for 3 days.

As a result, an adhesive film for backgrinding was obtained.

<Confirmation of basic properties>

(1) Adhesion evaluation: Measurement of adhesion before and after ultraviolet irradiation

(i) Preparation of adherend wafers for measurement of adhesion:

The mirror surface of a silicon mirror wafer (4-inch single-sided mirror wafer manufactured by SUMCO) was ozone cleaned using a UV ozone cleaning device (UV-208 manufactured by Techno Vision Transfer) (ozone treatment time: 60 seconds). Afterwards, the mirror surface of the wafer was wiped with ethanol and was used as an adherend wafer.

(ii) Measurement of adhesion before ultraviolet irradiation:

In an environment of 23°C and 50%RH, the adhesive film obtained in <Production of the adhesive film> is cut to a width of 50 mm, the separator is peeled off, and the adhesive film is spread through the adhesive resin layer using a hand roller. The complex was attached to the mirror surface of the wafer. Then, it was left for 1 hour.

After leaving, using a tensile tester (Shimadzu Seisakusho, product name: Autograph AGS-X), one end of the adhesive film is clamped, and the surface of the adherend wafer is applied at a peeling angle of 180° and a peeling speed of 300 mm/min. The adhesive film was peeled from the. The stress at this time was measured and converted to N/25mm, and the adhesive force was obtained. Evaluation was performed at N = 2, and the two obtained values were averaged and designated as peeling strength F0.

(iii) Measurement of adhesion after ultraviolet irradiation:

In an environment of 23°C and 50%RH, the adhesive film for adhesion evaluation is cut to a width of 50 mm, the separator is peeled off, and using a hand roller, the adhesive film is attached to the mirror surface of the adherend wafer through the adhesive resin layer. did. Then, it was left for 1 hour.

After leaving, the pressure-sensitive adhesive film was irradiated with ultraviolet rays with a main wavelength of 365 nm using a high-pressure mercury lamp at an irradiation intensity of 100 mW/cm ² and an amount of 1080 mJ/cm ² in an environment of 25°C. Afterwards, using a tensile tester (Shimadzu Seisakusho, product name: Autograph AGS-X), one end of the adhesive film is clamped, and the surface of the adherend wafer is peeled off at a peeling angle of 180° and a peeling speed of 300 mm/min. The adhesive film was peeled from the. The stress at this time was measured and converted to N/25mm to obtain the adhesive force. Evaluation was performed at N = 2, and the two obtained values were averaged and designated as peeling strength F1.

Then, F1/F0 was calculated from the obtained values of F1 and F0.

(2) Adhesive residue evaluation

In (iii) above, the adherend wafer after UV peeling was visually observed to determine the presence or absence of adhesive residue. When adhesive residue could not be confirmed, it was written as “none” in Table 1.

<Various evaluations of the free dicing method>

(1) Production of evaluation wafers

Evaluation wafer 1:

Using a dicing saw, half-cut the mirror surface of a mirror wafer (manufactured by KST World, 8-inch mirror wafer, diameter: 200 ± 0.5 mm, thickness: 725 ± 50 μm, single-sided mirror) to obtain an evaluation wafer. got 1 (Blade: ZH05-SD3500-N1-70-DD, chip size: 5mm×8mm, depth of cut: 58㎛, blade rotation speed: 30000rpm). Evaluation Wafer 1 was observed under an optical microscope, and the cuff width was 35 μm.

Evaluation Wafer 2:

Using a dicing saw, make a half cut in the first step on the mirror surface of the mirror wafer (manufactured by KST World, 8-inch mirror wafer, diameter: 200 ± 0.5 mm, thickness: 725 ± 50 ㎛, single-sided mirror). was performed (blade: Z09-SD2000-Y158×0.25A×40×45E-L, chip size: 5mm×8mm, depth of cut: 15㎛, blade rotation speed: 30000rpm). As observed with an optical microscope, the cuff width was 60 μm. Subsequently, a second half cut was performed (blade: ZH05-SD3500-N1-70-DD, chip size: 5 mm x 8 mm, depth of cut: 58 μm, blade rotation speed: 30000 rpm), and evaluation wafer 2 was obtained. .

(2) Implementation of free dicing method and various evaluations

Using a tape laminator (DR3000II, manufactured by Nitto Denko), an adhesive film was attached to the half-cut side of the evaluation wafer (evaluation wafer 1 or 2) (23°C, application speed: 5 mm/sec, application pressure: 0.36 MPa). ).

Subsequently, using a grinder (DGP8760, manufactured by DISCO), the back side of the wafer was ground (controlled cutting and precision cutting, precision cutting amount: 40 μm, no polish, thickness after grinding: 38 μm) and broken into pieces.

Afterwards, UV irradiation and peeling of the adhesive film were performed to evaluate device peelability and adhesive residue after the pre-dicing method.

Regarding UV irradiation, specifically, using a high-pressure mercury lamp in an environment of 25°C, the adhesive film was irradiated with ultraviolet rays with a main wavelength of 365 nm at an irradiation intensity of 100 mW/cm ² and an amount of 1080 mJ/cm ² of ultraviolet rays.

Peeling of the adhesive film was performed in the following procedure. First, using a wafer mounter (MSA300, manufactured by Nitto Denko), a separately prepared dicing tape (used as a mounting tape) was placed through the adhesive side of the dicing tape to form an 8-inch wafer ring frame and the above-described reorganization. It was attached to the wafer side of the converted wafer. Subsequently, the adhesive film for pre-dicing evaluation was peeled from the wafer notch using a tape peeler (HR3000III, manufactured by Nitto Denko) with a peeling tape (PET38REL, manufactured by Lasting Systems).

Then, the device peelability was evaluated. In Table 1, the case where the adhesive film for pre-dicing evaluation can be peeled from the wafer in one go is described as “OK”.

Additionally, the adhesive residue on the wafer that was separated into pieces after the pre-dicing method was observed and evaluated using an optical microscope (manufactured by Olympus). In the observation, it was observed whether there was any thread-like adhesive residue, especially in the portion where the groove had been previously provided. In Table 1, cases in which adhesive residue was not confirmed were described as “OK”, and cases in which adhesive residue was present were described as “present.”

Various information is integrated and shown in Table 1. The unit of E'(-15℃) and E'(100℃) is Pa.

As shown in Table 1, an ultraviolet curable adhesive resin material in which E'(100°C) and E'(100°C)/E'(-15°C) are within appropriate numerical ranges when manufacturing electronic devices by the free dicing method. By using an adhesive film having an adhesive resin layer composed of, the generation of adhesive residue was suppressed.

On the other hand, when manufacturing electronic devices by the free dicing method, part or all of E' (100°C) and E' (100°C)/E' (-15°C) were not within the appropriate value range for the ultraviolet curable adhesive resin material. When an adhesive film having an adhesive resin layer composed of was used, adhesive residue was generated.

This application claims priority based on Japanese Patent Application No. 2021-090297 filed on May 28, 2021, and the entire disclosure thereof is incorporated herein.

10: Base layer
20: Adhesive resin layer
30: wafer
30A: circuit forming surface
31: Chip
50: Adhesive film
100: structure

Claims (7)

A step (A) of preparing a structure comprising a wafer having a circuit formation surface and an adhesive film bonded to the circuit formation surface side of the wafer;
A step (B) of backgrinding a surface of the wafer opposite to the circuit formation surface,
Step (C) of irradiating the adhesive film with ultraviolet rays and then removing the adhesive film from the wafer
A method of manufacturing an electronic device comprising at least,
The adhesive film includes a base layer and an adhesive resin layer made of an ultraviolet curable adhesive resin material provided on one side of the base layer,
For the above ultraviolet curable adhesive resin material, the storage elastic modulus at -15°C when measuring the viscoelastic properties using the following procedures (i) and (ii) is E' (-15°C) and storage at 100°C. When the elastic modulus is E' (100℃),
E' (100°C) is 1.0×10 ⁶ to 3.5×10 ⁷ Pa,
E'(100℃)/E'(-15℃) is 2.0×10 ^-3 to 1.5×10 ^-2
Phosphorus, method of manufacturing electronic devices.
[Sequence]
(i) Form a film with a film thickness of 0.2 mm using the above ultraviolet curable adhesive resin material, and irradiate the film with ultraviolet rays with a dominant wavelength of 365 nm using a high-pressure mercury lamp in an environment of 25°C with an intensity of 100 W/cm ² By irradiating with an ultraviolet dose of 1080 mJ/cm ² and curing it with ultraviolet rays, a cured film is obtained.
(ii) For the cured film, the dynamic viscoelasticity is measured at a frequency of 1 Hz, in tensile mode, and at a temperature in the range of -50 to 200°C. The method of claim 1, wherein E' (-15°C) is 6.0×10 ⁸ to 3.0×10 ⁹ Pa. The method of claim 1 or 2, wherein the step (A) is
At least one process (A1) selected from the process (A1-1) of half-cutting the wafer and the process (A1-2) of irradiating the wafer with a laser and forming a modified layer on the wafer,
After the step (A1), a step (A2) of attaching the adhesive film to the circuit formation side of the wafer.
A method of manufacturing an electronic device comprising. The adhesive resin layer according to any one of claims 1 to 3, wherein in the step (C), the adhesive film is irradiated with ultraviolet rays at a dose of 200 mJ/cm ² or more and 2000 mJ/cm ^{2 or} less. A method of manufacturing an electronic device in which the adhesive strength of the adhesive resin layer is reduced by photocuring, and then the adhesive film is removed from the wafer. The method of manufacturing an electronic device according to any one of claims 1 to 4, wherein the adhesive resin layer contains a (meth)acrylic resin having a polymerizable carbon-carbon double bond in a molecule and a photoinitiator. The method of manufacturing an electronic device according to any one of claims 1 to 5, wherein the adhesive resin layer has a thickness of 5 μm or more and 300 μm or less. The resin according to any one of claims 1 to 6, wherein the resin constituting the base layer is polyolefin, polyester, polyamide, poly(meth)acrylate, polyvinyl chloride, polyvinylidene chloride, polyimide, One type selected from the group consisting of polyetherimide, ethylene/vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene, ionomer, polysulfone, polyethersulfone, polyetheretherketone, and polyphenyleneether. Or a method of manufacturing an electronic device comprising two or more types.

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